TW201903108A - Solvent based adhesive composition - Google Patents

Abstract

Solvent-based adhesive composition are disclosed, the compositions comprising (A) a polyester-urethane resin, (B) a phosphate ester compound, and (C) an aliphatic isocyanate curing agent. Methods for preparing a solvent-based adhesive composition, the methods comprising providing a polyester-urethane resin, providing a phosphate ester compound, mixing the polyester-urethane resin and phosphate ester compound to form a resin mixture, diluting the resin mixture in a solvent to form a diluted resin mixture having an application solid content of from 25 to 55 weight percent, based on the total weight of the diluted resin mixture, and curing the diluted resin mixture with an aliphatic isocyanate curing agent at a mix ratio (parts by weight resin mixture before dilution: parts by weight aliphatic isocyanate curing agent) of from 100:1 to 100:12. Laminates prepared comprising the solvent-based adhesives and according to the disclosed methods are also disclosed.

Description

Solvent-based adhesive composition

The present invention relates to a solvent-based adhesive composition. More specifically, the present invention relates to solvent-based adhesive compositions for use in, for example, high-performance laminating adhesive applications, which compositions exhibit improved adhesion to metal structures such as foils, and improved heat resistance and Chemical resistance. The solvent-based adhesive composition includes a polyester-urethane resin modified with a phosphate compound and an aliphatic isocyanate curing agent. The invention further relates to a method for preparing such a solvent-based adhesive composition.

The adhesive composition is suitable for various purposes. For example, some adhesives are used to adhere the layers of the substrate together, thereby forming a layered structure including two or more substrate layers. A flexible packaging laminated adhesive is applied between the laminated films for packaging food, pharmaceuticals and industrial consumer products. Laminating adhesives can generally be divided into three categories: (1) solvent-based laminating adhesives, (2) solvent-free laminating adhesives, and (3) water-based laminating adhesives. Within the solvent-based category, solvent-based polyurethanes have been widely used to achieve relatively good heat resistance, moisture resistance, and chemical resistance.

Solvent-based adhesive compositions can be used in high-performance layered product applications (such as retorts, hot cans, cooking bags, etc.). To achieve the high performance required for such applications, polyester systems containing epoxidized bisphenol A are commonly used. The use of bisphenol A epoxy resins has recently encountered regulatory and user challenges regarding the perceived safety of bisphenol A based materials for food packaging.

Therefore, there is a need for a bisphenol A-free adhesive composition suitable for high-performance applications, especially for laminated structures used in high-performance applications.

Disclosed herein are solvent-based adhesive compositions. In some embodiments, the solvent-based adhesive composition includes: a first part including (A) a polyester-urethane resin and (B) a phosphate compound and a (C) aliphatic isocyanate curing agent the second part. The aliphatic isocyanate curing agent (C) of the second part crosslinks the components of the first part. In some embodiments, the phosphate compound has structure (I): (I) wherein R ¹ is any organic group.

A method for preparing a solvent-based adhesive composition is also disclosed. The method includes providing a polyester-urethane resin, providing a phosphate ester compound, mixing the polyester-urethane resin and the phosphate ester compound to form a resin mixture, and diluting the resin mixture in a solvent to form A diluted resin mixture having an applied solid content of 25 to 55 weight percent based on the total weight of the diluted resin mixture, and a mixing ratio of 100: 1 to 100: 12 (parts by weight of the resin mixture before dilution: aliphatic Isocyanate curing agent parts by weight) The diluted resin mixture is cured with an aliphatic isocyanate curing agent.

The disclosed adhesive composition is bisphenol A-free and is particularly suitable for laminated structures used in high-performance food packaging applications, such as retort applications, hot-fill applications, and retort pouch applications. The disclosed adhesive composition is particularly suitable for laminated structures used in high performance applications.

The solvent-based adhesive composition disclosed herein is suitable for a laminated structure including two or more flexible or rigid substrates. In some embodiments, the substrate may comprise a low- or medium-density plastic (eg, selected from polystyrene, polyethylene, ABS, polyurethane, polyethylene terephthalate, polyterephthalate Types of butyl, polypropylene, polybenzene, polycarbonate, polyacrylate, polyvinyl chloride, polyfluorene or mixtures thereof), paper, wood and recovered wood products, polymer coated substrates, wax coated Cardboard, cardboard, particle board, textiles, leather and metals (such as aluminum, ferrous iron and other non-ferrous iron), metalized plastics (such as metalized plastic films), or the like. In some embodiments, a laminated structure prepared using the disclosed solvent-based adhesive composition may include multiple layers / substrates, each layer / substrate being any of the materials described herein and the like.

The adhesive composition is particularly suitable for being subjected to retort treatment (for example, exposure to 120 ° C or higher for 30 minutes or more), hot filling treatment (for example, exposure to 66 ° C or higher for 30 minutes or more), and cooking Laminated structure for bag treatment (eg, exposure to 100 ° C. or higher for 30 minutes or more) (ie, high performance applications). In some embodiments, the solvent-based adhesive composition can be used in metal food packaging applications, such as deep drawn cans and containers with metal closures or flexible heat-sealed closures. In some embodiments, the solvent-based adhesive composition can be used in food pouches, ready-to-eat food, can coatings, and the like.

In some embodiments, the solvent-based adhesive composition includes: a first part including (A) a polyester-urethane resin and (B) a phosphate compound and a second part including (C) an aliphatic isocyanate section. The aliphatic isocyanate curing agent (C) of the second part crosslinks the components of the first part, thereby producing a polyester-urethane-polyurethane polymer network.

The two parts of the disclosed adhesive composition are mixed before contacting the substrate (for example when applied on a laminating machine). The mixed adhesive is applied to one substrate and dried before applying another layer of substrate. The layered article can then be cured at ambient or elevated temperatures. A first portion :( A) a polyester - urethane resin

In some embodiments, the solvent-based adhesive composition includes a first portion including (A) a polyester-urethane resin. In some embodiments, the polyester-urethane resin is a hydroxy-terminated polyurethane resin. Suitable hydroxy-terminated polyurethane resins can be prepared via the reaction of isocyanates (such as monomeric isocyanates and / or polyisocyanates) and polyester polyols. As used herein, a "polyisocyanate" is any compound containing two or more than two isocyanate groups. For example, the polyisocyanate may include a dimer, a trimer, and the like. In such reactions, the polyester polyol is present in excess in order to produce a hydroxyl-terminated polyurethane resin, in other words, the stoichiometric ratio of hydroxyl to isocyanate groups should be higher than one.

Suitable isocyanates of the present invention include, but are not limited to, aromatic isocyanates, aliphatic isocyanates, cycloaliphatic isocyanates, and combinations of two or more thereof. An "aromatic isocyanate" is an isocyanate containing an isocyanate group bonded to an aryl group and containing one or more aromatic rings. An "aliphatic polyisocyanate" is an isocyanate containing an isocyanate group (which can be bonded to other aliphatic groups), a cycloaliphatic group, or an aromatic ring (group) bonded to an aliphatic group. "Cycloaliphatic polyisocyanates" are a subgroup of aliphatic isocyanates in which the chemical chain is ring-structured.

Suitable aromatic isocyanates include, but are not limited to, 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 1,5-naphthyl diisocyanate, and diisocyanate. Acid 2,6-tolyl ester ("2,6-TDI"), 2,4-tolyl diisocyanate ("2,4-TDI"), 2,4'-diphenylmethane diisocyanate (" 2,4′-MDI ”), 4,4′-diphenylmethane diisocyanate (“ 4,4′-MDI ”), 3,3′-dimethyl-4,4′-biphenyl diisocyanate ( "TODI") or a mixture of two or more of them.

Suitable aliphatic isocyanates have 3 to 16 carbon atoms or 4 to 12 carbon atoms in a linear or branched alkylene residue, such as hexamethylene diisocyanate (" HDI ") , 1,4- Diisocyanate butane, 1,3-xylyl diisocyanate ("1,3-XDI") and 1,4-xylyl diisocyanate ("1,4-XDI"). Suitable cycloaliphatic isocyanates have 4 to 18 carbon atoms or 6 to 15 carbon atoms in the cycloalkylene residue. Cycloaliphatic diisocyanate refers to ring-bound and aliphatic-bound NCO groups, such as isophorone diisocyanate ("IPDI"), 1,3 / 1,4-diisocyanate cyclohexane 1,3- / 1, 4-bis (isocyanatomethyl) cyclohexane and diisocyanatodicyclohexylmethane ("H ₁₂ MDI").

Suitable aliphatic and cycloaliphatic isocyanates include, but are not limited to, cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethyl Cyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate, such as Methyl-1,8-octane diisocyanate ("TIN"), decane diisocyanate and decane triisocyanate, undecane diisocyanate and undecane triisocyanate, and dodecane diisocyanate and dodecane triisocyanate Isocyanate, isophorone diisocyanate ("IPDI"), hexamethylene diisocyanate ("HDI"), diisocyanate dicyclohexylmethane ("H ₁₂ MDI"), 2-methylpentane diisocyanate ("MPDI"), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate ("TMDI"), norbornane Diisocyanate ("NBDI"), diisocyanate Acid ditolyl ester ("XDI"), tetramethyl ditolyl diisocyanate, and dimers, trimers, and mixtures of two or more thereof.

Additional isocyanates suitable according to the invention include, but are not limited to, 4-methyl-cyclohexane 1,3-diisocyanate, 2-butyl-2-ethylpentyl diisocyanate, and isocyanate 3 (4 ) -Isocyanate methyl-1-methylcyclohexyl, 2-isocyanate propylcyclohexyl isocyanate, 2,4′-methylene bis (cyclohexyl) diisocyanate, 1,4-diiso 4-methyl-pentane cyanate and a mixture of two or more thereof.

As used herein, "polyol" refers to a compound having two or more hydroxyl groups (ie, -OH) per molecule. As used herein, "ester" refers to a compound containing an ester bond. As used herein, "polyester" refers to a compound containing two or more ester bonds per molecule. The compound of polyester and polyol is "polyester polyol". An aliphatic polyester polyol is a polyester polyol which does not contain an aromatic ring in its molecule. Aromatic polyester polyols are polyester polyols that contain one or more aromatic rings in their molecules.

In some embodiments, the polyester-urethane resin accounts for 65 to 99.5 weight percent of the total weight of the polyester-urethane resin (A) and the phosphate ester (B). In some embodiments, the polyester-urethane resin accounts for 95 to 99 weight percent of the total weight of the polyester-urethane resin (A) and the phosphate ester (B).

Commercially available examples of polyester-urethane resins suitable for use in accordance with the present invention include ADCOTE ™ 811A EA, which is available from The Dow Chemical Company. Part I : ( B ) Phosphate Ester Compound

In some embodiments, the solvent-based adhesive composition includes a first portion including (B) a phosphate compound. Without being bound by theory, it is believed that the polyester-urethane resin (A) and the phosphate compound (B) react with the isocyanate curing reagent (C) via a reaction between a hydroxyl group and an isocyanate functional group. To produce a uniform polyester-urethane-polyurethane network. In addition, the phosphate functional group of the phosphate compound reacts / complexes with a reactive site on a metal film, a metal oxide-coated film, or a polymer film to improve adhesion.

In some embodiments, the phosphoric acid ester compound accounts for 0.5 to 35 weight percent of the total weight of the polyester-urethane resin (A) and the phosphoric acid ester compound (B). In some embodiments, the phosphate ester is 0.5 to 5 weight percent of the total weight of the polyester-urethane resin (A) and the phosphate ester compound (B).

In some embodiments, the phosphate compound has structure (I): (I) wherein R ¹ is any organic group. In addition to the pendant groups shown in Structure (I), R ¹ may or may not have one or more additional pendant -OH groups, and R ¹ may or may not have one or more additional pendants of Structure (I) base. Any two or more of the -OH group and the group of structure (I) may or may not be connected to the same atom of R ¹ . Preferably, each -OH group and each group in structure (I) are connected to a separate atom of R ¹ .

A suitable way to characterize R ¹ is to describe a compound having structure (II): (II) where R ¹ is the same as in structure (I). Compounds having structure (II) are known herein as "precursor polyols".

In some embodiments, a suitable precursor polyol has a number average molecular weight of 90 or higher, or 200 or higher, or 400 or higher. In some embodiments, a suitable precursor polyol has a number average molecular weight of 4,000 or less, or 2,000 or less, or 1,200 or less, or 900 or less, or 500 or less. In some embodiments, a suitable precursor polyol has a number average molecular weight of 200 to 4,000, or 400 to 2,000, or 400 to 1,200, or 400 to 900.

In some embodiments, suitable precursor polyols are higher alkyl polyols, monosaccharides, disaccharides, and compounds having structure (III): (III) wherein each of R ² , R ³ , R ⁴ and R ⁵ is independently any organic group; each of n ₁ , n ₂ and n ₃ is independently 0 to 10 each Integer. In addition to the pendant groups shown in structure (III), R ² may or may not have one or more additional pendant groups. It is further understood that any two or more of the pendant groups may or may not be attached to the same atom of R ² . In some embodiments, there is a mixture of compounds having the structure (III), wherein the values of one or more of n ₁ , n _2, and n ₃ of the compound of the structure (III) are different from each other. Such mixtures are described herein by describing the non-integer values of the parameters n ₁ , n ₂ or n ₃ , where the non-integer values represent the average number of the parameters. When it is necessary to evaluate the molecular weight of such a mixture, a number average molecular weight is used.

In the precursor polyol having structure (III), preferably, each pendant group is connected to a separate atom of R ² .

In the precursor polyol having structure (III), preferably, one or more of R ³ , R ⁴ and R ⁵ are those having 1 to 4 carbon atoms, or 2 to 3 carbon atoms, or 3 Hydrocarbon group of 1 carbon atom. In the precursor polyol having structure (III), preferably, one or more of R ³ , R ⁴ and R ⁵ is an alkyl group, which may be linear or cyclic or branched or a combination thereof ; More preferably, one or more of R ³ , R ^4, and R ⁵ are linear or branched alkyl groups; more preferably, one or more of R ³ , R ^4, and R ⁵ are branched alkanes; base. Preferably, R ³ , R ⁴ and R ⁵ are the same as each other.

In the precursor polyol having the structure (III), preferably, one or more of n ₁ , n ₂ and n ₃ are 0 to 8. In the precursor polyol having the structure (III), it is preferable that one or more of n ₁ , n ₂ and n ₃ is 1 or more. In the precursor polyol having the structure (III), it is preferable that one or more of n ₁ , n ₂ and n ₃ is 6 or less. In the precursor polyol having the structure (III), preferably, n ₁ , n ₂ and n ₃ are the same as each other.

A preferred group of precursor polyols having structure (III) are compounds in which each of R ² , R ³ , R ^4, and R ⁵ is an alkyl group; such precursor polyols are known herein Is an alkoxylated alkyltriol. In triol, when at least one of n ₁ , n ₂ and n ₃ is 1 or more and R ² has a structure (IV): (IV) The triol is known herein as an alkoxylated glycerol. In alkoxylated triols, when each of R ³ , R ⁴ and R ⁵ is a branched chain alkyl group having exactly 3 carbon atoms, the alkoxylated triol is known herein as prop Oxytriol. A propoxylated triol (wherein R ² has the structure (IV)) is known herein as a propoxylated glycerol.

Among the precursor polyols which are higher alkyl polyols, those having 10 or fewer carbon atoms are preferred; those having 6 or fewer carbon atoms are more preferred; Those of 3 or less carbon atoms; more preferably glycerol.

More preferred precursor polyols are higher alkyl polyols and compounds having structure (III). It should be noted that if n ₁ = n ₂ = n ₃ = 0 and R ² is an alkyl group or an alkyl group having a hydroxyl group, the compound having the structure IV is an alkyl higher polyol.

Preferred groups of precursor polyols are alkyltriols and alkoxylated alkyltriols. Of these, glycerol and alkoxylated glycerol are more preferred; alkoxylated glycerol is more preferred. Among the alkoxylated glycerols, propoxylated glycerol is preferred.

Another class of suitable phosphate compounds are those containing urethane bonds. Phosphate compounds containing urethane bonds are prepared by reacting one or more suitable phosphate-functional polyols with one or more polyisocyanates, preferably containing one or more diisocyanates. Preferably, the amount of polyisocyanate is kept low enough that some or all of the reaction products are phosphate-functional polyols. Alternatively, the polyol may be first reacted with a polyisocyanate to make an -OH terminated prepolymer which is then reacted with polyphosphoric acid. A phosphate compound having a urethane bond will have a number average molecular weight in the range of 1,000 to 6,000, preferably in the range of 1,200 to 4,000, and more preferably in the range of 1,400 to 3,000.

In some embodiments, the phosphate compound is a reactant comprising a precursor polyol and a phosphoric acid-type acid, and a reaction product of a phosphate compound having structure (I).

Preferably, the amount of phosphoric acid and precursor polyol is selected to determine the ratio of M _p : M _x as follows: M _hy = number of hydroxyl groups per molecule of precursor polyol N _x = M _hy -2 M _x = (precursor Polyol Morr) × (N _x ) M _p = Morr of phosphorus atom contained in phosphoric acid

In some embodiments, the ratio of M _p : M _x is 0.1: 1 or higher, or 0.2: 1 or higher, or 0.5: 1 or higher, or 0.75: 1 or higher. In some embodiments, the ratio of M _p : M _x is 1.1: 1 or less.

In some embodiments, the weight ratio of phosphoric acid-type acid to precursor polyol is 0.005: 1 or higher, or 0.01: 1 or higher, or 0.02: 1 or higher. In some embodiments, the weight ratio of phosphoric acid-type acid to precursor polyol is 0.3: 1 or less, or 0.2: 1 or less, or 0.12: 1 or less.

In some embodiments, the phosphoric acid contains a polyphosphoric acid. In some embodiments, the amount of polyphosphoric acid in the phosphoric acid-type acid is 75 wt% or more, or 80 wt% or more, or 90 wt% or more based on the weight of the phosphoric acid. Various grades of polyphosphoric acid are available; each grade is characterized by percentage. In order to determine the grade, it was first recognized that the content of pure monomer orthophosphoric acid and phosphorus pentoxide was considered to be 72.4%. Polyphosphoric acid of any grade can also be analyzed to consider the molar number of a mole polyphosphoric acid (molecular weight marker "Fppa") containing phosphorus pentoxide labeled "Nppo", and given by PCppo = (Nppo × 142) / Fppa Percent phosphorus oxide ("PCppo") expressed as a percentage. The polyphosphoric acid grade is then a ratio, expressed as a percentage: grade = PCppo / 72.4.

In some embodiments, polyphosphoric acid having a grade of 100% or higher, or 110% or higher is used. In some embodiments, polyphosphoric acid having a grade of 150% or less, or 125% or less is used.

In some embodiments, in addition to one or more phosphate-functional polyols, the disclosed solvent-based adhesive composition also contains one or more phosphorus-free polyols.

Additional information on suitable phosphates and their preparation can be found in PCT Publication No. WO / 2015/168670, which is incorporated herein by reference in its entirety. Part II: ( C ) aliphatic isocyanate curing agent

In some embodiments, the solvent-based adhesive composition includes a second portion including an aliphatic isocyanate curing agent (C). In some embodiments, the polyester-urethane resin (A) and the phosphate compound (B) are combined to form a resin mixture. The resin mixture is diluted in a solvent to form a diluted resin mixture having an applied solid content of 25 to 55 weight percent, or 30 to 45 weight percent, or 35 to 40 weight percent based on the total weight of the diluted resin mixture. The diluted resin mixture may then be cured with an aliphatic isocyanate curing agent (C) at a mixing ratio of 100: 1 to 100: 12 (parts by weight of the resin mixture before dilution: parts by weight of the aliphatic isocyanate curing agent).

The aliphatic isocyanate used may be any suitable aliphatic isocyanate. Suitable aliphatic isocyanates include, but are not limited to, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate ( Such as 4-isocyanatomethyl-1,8-octane diisocyanate ("TIN"), decane di and triisocyanate, undecane di and triisocyanate, dodecane di and triisocyanate, isophorone di Isocyanate ("IPDI"), diisocyanate adipate ("HDI"), diisocyanate dicyclohexylmethane ("H ₁₂ MDI"), 2-methylpentane diisocyanate ("MPDI") 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate ("TMDI"), norbornane diisocyanate ("NBDI "), Dimethyl diisocyanate (" XDI "), tetramethylxylyl diisocyanate, and dimers, trimers, and mixtures of two or more thereof.

As collected from the foregoing, the present invention contemplates the use of two parts, which are preferably mixed using a suitable mixer (such as an electric, pneumatic, or otherwise powered mechanical mixer) before or during coating to the substrate to form an adhesive剂 组合 物。 Composition. Mixing can occur at any suitable time in the process, such as before, during, or as a result of the coating process. All steps of the invention can be carried out at ambient room temperature. Heating or cooling can be used as required.

Methods for preparing solvent-based adhesive compositions are disclosed herein. In some embodiments, a polyester-urethane resin is provided, a phosphate compound is provided, the polyester-urethane resin and the phosphate compound are mixed to form a resin mixture, and the resin mixture is diluted in a solvent to form A diluted resin mixture having an applied solid content of 25 to 55 weight percent, or 30 to 45 weight percent, or 35 to 40 weight percent, based on the total weight of the diluted resin mixture, and 100: 1 to 100: 12 , Or a mixing ratio of 100: 4 to 100: 10 (parts by weight of the resin mixture before dilution: parts by weight of the aliphatic isocyanate curing agent) the diluted resin mixture is cured with the aliphatic isocyanate curing agent.

The disclosed adhesive composition is suitable for bonding substrates together. The substrate may be a similar material or a different material. Wet and dry adhesive lamination of a plurality of substrate layers is possible. The disclosed adhesive composition can be applied to a desired substrate using conventional coating techniques such as rotogravure printing, flexible letterpress printing, conventional or airless spraying, roll coating, brush coating, Winding rod coating, doctor blade coating or coating processes such as curtain coating, overflow coating, bell coating, dish coating and dip coating. Coating with an adhesive composition may be performed on the entire surface or only a portion thereof, such as along the edges or in intermittent locations. Once applied to the substrate, the composition is dried, such as by applying heat and air flow, or some other suitable route, to remove substantially all of the remaining solvent.

The disclosed adhesive composition can be used on a wide variety of one or more suitable substrates, such as high, low, or medium density plastics (eg, selected from the following types: polystyrene, polyethylene, ABS, Polyurethane, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polybenzene, polycarbonate, polyacrylate, polyvinyl chloride, polyfluorene, or mixtures thereof), Paper, wood and recovered wood products, polymer-coated substrates, wax-coated cardboard, cardboard, particle board, fabrics, leather, and metals (such as aluminum, ferrous and other non-ferrous), Metallized plastic (such as metallized plastic film) or similar. Adhesive compositions are particularly attractive for packaging and sealing applications. For example, a plastic film, metal film, or metallized plastic film can be laminated (eg, on all or at least a portion of its surface, such as along its edges or at intermittent locations) with the adhesive composition of the present invention. In some embodiments, the food can be packaged for cooking bag preparation, or the resulting layered article can be used to seal or encapsulate some other article. When a large-size foil is used in a laminated structure, the resulting layered product can be cold-drawn to produce a cup or package that can be filled with food, and then covered and sealed with a similar laminated structure to form a sealed container.

For the cold drawability and best performance of the adhesive system, it is important that the final laminated structure has balanced mechanical properties. Balanced mechanical properties will allow load and stress to be distributed on the layered product under conditions of manufacture and use of the layered product with temperature changes. Phosphate-based adhesives can provide laminates with improved mechanical properties to balance and transfer loads and stresses within the laminated structure. The storage modulus of cured pure polyester-urethane-polyurethane with or without phosphate ester additives will be about 50 to 1,500 MPa (at 0 ° C) and 0.7 to 6.0 MPa ( At 25 ° C) and 0.10 to 1.50 (at 60 ° C). An important performance difference will be the percent elongation of the laminated structure as a function of orientation. The elongation% in the longitudinal and transverse directions will be more balanced in both directions, in the range of 8.0 to 10.5%, and the difference between the longitudinal and transverse directions will be an absolute value of about 0.0 to 0.30%, due to the phosphate ester The ability to interact with the substrate surface and help balance the difference in force distribution across the laminated structure.

The invention will now be described in further detail by discussing illustrative examples ("IE") and comparative examples ("CE") (collectively "examples"). However, the scope of the present invention is of course not limited to IE. Raw materials

The examples are prepared using raw materials including polyester-polyurethane resins available under the trade name ADCOTE ™ 811A EA from The Dow Chemical Company, and trade names MOR-FREE ™ 200C And ADCOTE ™ 811B are aliphatic isocyanate curing agents available from The Dow Chemical Company, polyether polyols available from the Dow Chemical Company under the trade name VORNAOL ™ CP 450, and isocyanates available from the Dow Chemical Company under the trade name ISONATE ™ 125M 11.115% polyphosphoric acid available from Sigma-Aldrich and ethyl acetate and methyl ethyl ketone available from Sigma-Aldrich.

Acid value (AV) is measured by ASTM D 3655-06 (American Society for Testing and Materials, West Conshohocken, PA, USA).

The number of hydroxyl groups (OHN) was measured by ASTM D 4274-88 (American Society for Testing and Materials, West Conshohocken, PA, USA).

Size exclusion chromatography (SEC) uses two PLgel Mix-B and PLgel Mixed-D columns and a Viscotek triple detector. Polystyrene standards were used to generate universal calibration curves to determine weight average molecular weight and number average molecular weight. Prior to analysis, samples were diluted with THF to a polymer concentration of approximately 2.5 mg / ml.

Solution viscosity was measured according to method ASTM D2196-10 (ASTM; West Conshohocken, PA, USA), using Brookfield viscosity measurement.

The example was prepared using a film comprising: Prelam, which is laminated at 3.26 g / m ² (2.00 pounds /) into 12 μm (48 gauge) of 0.00035 mil aluminum foil with ADCOTE ™ / co-reactant F ) Polyester ("PET") film, available from The Dow Chemical Company; 1.5 gauge aluminum foil; and cast polypropylene ("CPP") film with a thickness of 1 or 2 mils. Preparation of phosphate ester adhesion promoter

The 1 L multi-neck round bottom flask was dried in an oven, rinsed with dry N _{2 for} 30 minutes, then charged with 150 g of VORANOL ™ CP 450 polyether polyol and placed under a N ₂ purge at 70 mL / min. The syringe was loaded with 4 grams of 115% polyphosphoric acid (PPA). PPA was added dropwise to the polyether polyol under vigorous agitation. An extremely small temperature increase was observed. The reactor contents were heated to 100 ° C for 1 hour and then cooled to 45 ° C. Add 40 grams of ethyl acetate, then slowly add 50 grams of ISONATE ™ 125 M diisocyanate. A significant exotherm was controlled by applying an ice batch to keep the reaction tank below 75 ° C and a yellow to amber development was observed. The reactor was then maintained at 65 ° C for 1 hour, at which time the contents were cooled and sealed. The product has the following characteristics: 76.0% solids, 112 mg KOH / g OOH, 19.0 mg KOH / g AV, viscosity of 1665 mPa · s at 25 ° C, SEC analysis of Mn 1700, Mw 4100, polydispersity of 2.4 , 4.4% ≤ 500 Daltons, and 16.0% ≤ 1000 Daltons.

Detailed adhesive formulations containing comparative examples ("CE") and illustrative examples ("IE") of the relevant raw materials are summarized in Table 1. Table 1: Adhesive formulations for CE1, CE2, CE3 and IE1 to IE5 Preparation of pure adhesive castings and DMA / DSC characteristics

A variety of polyester-urethane and polyester-urethane / phosphate compound blend systems are cured with aliphatic isocyanate curing agents at various mixing ratios. An adhesive was prepared by taking about 15 grams of a polyester-urethane and polyester-urethane / phosphate compound blend solution and mixing it with an aliphatic isocyanate in a bottle at various mixing ratios. casting. The adhesive solution was mixed for about 15 to 30 minutes, and then poured into a polymethylpentene petri dish. The solvent was allowed to evaporate on a horizontal surface in a fume hood overnight, and then the casting was placed in a convection oven and cured at 45 ° C. for 7 days.

The castings were analyzed via DMA (TA Instruments Q800) using a multi-frequency strain mode. From -100 ° C to 150 ° C, a single applied frequency of 1 Hz is used, the heating rate is 3 ° C / min, the applied stress is 0.01%, and a preload force of 0.01 N is used.

The glass transition temperature (Tg) was measured using a TA instrument company Q100 DSC with an automatic sampler and RCS connected to a desktop computer using Q series software. Approximately 10 mg of the sample was placed in a t-zero plate with an aluminum closed lid. The samples were operated using the following conditions: Initial heat: 80 ° C for 5 minutes. Initial heat: -85 ℃ × 10 ℃ / min => 200 ℃. Cooling cycle: 200 ℃ × 10 ℃ / min = ＞-85 ℃. 2 ^nd heat: -85 ° C × 10 ° C / min => 240 ° C; return to room temperature.

Via a second DSC heating cycle reported T _g.

The important characteristics of the analyzed samples are summarized in Table 2. A homogeneous polymer network with well-maintained mechanical properties is formed by introducing a phosphate ester adhesion promoter into the system. The storage modulus of cured pure polyester-urethane-polyurethane with or without phosphate ester additives will be about 50 to 1,500 MPa (at 0 ° C) and 0.7 to 6.0 MPa ( At 25 ° C) and 0.10 to 1.50 (at 60 ° C). Table 2: DMA characteristic results Study on Adhesive Lamination

A variety of polyester-urethane and polyester-urethane / phosphate compound blend systems are cured with aliphatic isocyanate curing agents at various mixing ratios. The composition of the adhesive formulation is summarized in Table 1. The adhesive solution was mixed for about 15 to 30 minutes, and then coated on the Prelam with a Mayer rod to produce a coating weight of about 4.48 to 4.88 g / m ² (2.75 to 3.00 lb / ream), and then Laminate onto a 2 mil CPP film using a rolling temperature of 82 ° C. The layered article was cured in a convection oven at 45 ° C for up to 14 days.

The adhesive bonding strength was measured on a 15 mm wide layered strip on a Thwing-Albert tensile tester (model QC-3A) using a 50 Newton load cell (Newton load cell) at a rate of 10.0 cm / min. The following abbreviations are used to describe the test results: "AS" is the adhesive shunt, "FT" is the film tear, "FS" is the film extension, "AT" is the adhesive transfer, and "AF" is the adhesion failure.

The tensile properties of the laminated product were determined by inspecting the elongation percentage of the laminated product (foil / CPP) in the longitudinal and transverse directions using an Instron tensile tester on a laminated product strip of 25.4 mm × 175 mm. The test conditions of the Instron tensile tester are: the gap of the fixture is 7.62 cm, the dynamometer is 0-50 Newtons, the elongation rate (head speed) is 5.08 cm / min, and the elongation at break (%) is recorded.

Typical bond strength data and% elongation data are summarized in Table 3.

An important performance difference will be the percent elongation of the laminated structure as a function of orientation. The elongation% in the longitudinal and transverse directions will be more balanced in both directions, in the range of 8.0 to 10.5%, and the difference between the longitudinal and transverse directions will be an absolute value of about 0.0 to 0.30%, due to the phosphate The ability to interact with the substrate surface and help balance the difference in force distribution across the laminated structure. Table 3: Summary of adhesive strength and elongation% data a) Laminated structure: Prelam / 2 mil CPP b) Laminated structure: 1.5 gauge foil / 1 mil CPP, Trans: transverse direction, Mach: longitudinal direction

In addition to the embodiments described above and the examples described in the examples, many embodiments of specific combinations fall within the scope of the present invention, some of which are described below:

Example 1. A solvent-based adhesive composition comprising: (A) a polyester-urethane resin; (B) a phosphate ester compound; and (C) an aliphatic isocyanate curing agent.

Embodiment 2. The solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein the polyester-urethane resin is a reaction product of a polyester polyol and an isocyanate.

Embodiment 3. The solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein the polyester-urethane resin accounts for the polyester-urethane resin (A) and the phosphate ester (B) 65 to 99.5 weight percent of the total weight.

Embodiment 4. The solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein the polyester-urethane resin accounts for the polyester-urethane resin (A) and the phosphoric acid 95 to 99 weight percent of the total weight of the ester (B).

Embodiment 5. The solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein the phosphate ester compound accounts for the total of the polyester-urethane resin (A) and the phosphate ester (B) 0.5 to 35 weight percent.

Embodiment 6. The solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein the phosphate ester compound accounts for the total of the polyester-urethane resin (A) and the phosphate ester (B) 1 to 5 weight percent.

Embodiment 7. The solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein the phosphate compound has the structure (I): (I) wherein R ¹ is any organic group.

Embodiment 8. The solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein R ¹ has the structure (II): (II) where R ¹ is the same as in structure (I).

Embodiment 9. The solvent-based adhesive composition of any preceding or subsequent embodiment, wherein the phosphate compound comprises a urethane bond.

Example 10. The solvent-based adhesive composition of any of the foregoing or subsequent examples, further comprising a solvent.

Embodiment 11. The solvent-based adhesive composition of any preceding or subsequent embodiment, wherein the solvent is selected from the group consisting of ethyl acetate, methyl ethyl ketone, methyl acetate, and combinations thereof.

Embodiment 12. A method for preparing a solvent-based adhesive composition, the method comprising: providing a polyester-urethane resin; providing a phosphate ester compound; and applying the polyester-urethane resin And the phosphate ester compound are mixed to form a resin mixture; the resin mixture is diluted in a solvent to form a diluted resin mixture having an application solid of 25 to 55 weight percent based on the total weight of the diluted resin mixture Content; and the diluted resin mixture is cured with an aliphatic isocyanate curing agent at a mixing ratio of 100: 1 to 100: 12 (parts by weight of resin mixture before dilution: parts by weight of aliphatic isocyanate curing agent).

Embodiment 13. The method for preparing a solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein the diluted resin mixture has a weight percentage of 35 to 40 based on the total weight of the diluted resin mixture Application of solid content.

Embodiment 14. The method for preparing a solvent-based adhesive composition according to any of the foregoing or subsequent embodiments, wherein the mixing ratio (parts by weight of resin mixture before dilution: parts by weight of aliphatic isocyanate) is 100: 4 to 100 : 10.

Embodiment 15. A layered structure comprising the adhesive composition of any of the foregoing or subsequent embodiments.

Embodiment 16. The layered structure according to any of the foregoing or subsequent embodiments, further comprising a metal substrate.

Embodiment 17. The layered structure according to any of the foregoing or subsequent embodiments, further comprising a polyolefin substrate.

Claims (17)

A solvent-based adhesive composition includes: (A) a polyester-urethane resin; (B) a phosphate compound; and (C) an aliphatic isocyanate curing agent. The solvent-based adhesive composition as described in any of the foregoing or subsequent patent applications, wherein the polyester-urethane resin is a reaction product of a polyester polyol and an isocyanate. The solvent-based adhesive composition according to any of the foregoing or subsequent patent applications, wherein the polyester-urethane resin accounts for the polyester-urethane resin (A) and the phosphate ester (B) 65 to 99.5 weight percent of the total weight. The solvent-based adhesive composition according to any of the foregoing or subsequent patent applications, wherein the polyester-urethane resin accounts for the polyester-urethane resin (A) and the phosphate ester (B) 95 to 99 weight percent of the total weight. The solvent-based adhesive composition according to any of the foregoing or subsequent patent applications, wherein the phosphate ester compound accounts for the total weight of the polyester-urethane resin (A) and the phosphate ester (B) 0.5 to 35 weight percent. The solvent-based adhesive composition according to any of the foregoing or subsequent patent applications, wherein the phosphate ester compound accounts for the total weight of the polyester-urethane resin (A) and the phosphate ester (B) 1 to 5 weight percent. The solvent-based adhesive composition as described in any of the foregoing or subsequent patent applications, wherein the phosphate compound has the structure (I): (I) wherein R ¹ is any organic group. The solvent-based adhesive composition as described in the scope of any preceding or subsequent application patent, wherein R ¹ has the structure (II): (II) where R ¹ is the same as in structure (I). The solvent-based adhesive composition as described in the scope of any preceding or subsequent application patent, wherein the phosphate compound includes a urethane bond. A solvent-based adhesive composition as described in any of the foregoing or subsequent patent applications, further comprising a solvent. A solvent-based adhesive composition as described in the scope of any preceding or subsequent application patent, wherein the solvent is selected from the group consisting of ethyl acetate, methyl ethyl ketone, methyl acetate, and combinations thereof. A method for preparing a solvent-based adhesive composition, the method comprising: providing a polyester-urethane resin; providing a phosphate ester compound; adding the polyester-urethane resin and the phosphoric acid Ester compounds are mixed to form a resin mixture; the resin mixture is diluted in a solvent to form a diluted resin mixture having an applied solids content of 25 to 55 weight percent based on the total weight of the diluted resin mixture; and A mixing ratio of 100: 1 to 100: 12 (parts by weight of the resin mixture before dilution: parts by weight of the aliphatic isocyanate curing agent) the diluted resin mixture is cured with an aliphatic isocyanate curing agent. A method for preparing a solvent-based adhesive composition as described in the scope of any preceding or subsequent application patent, wherein said diluted resin mixture has a content of 35 to 40 weight percent based on the total weight of said diluted resin mixture. Apply solids content. The method for preparing a solvent-based adhesive composition as described in any of the foregoing or subsequent patent applications, wherein the mixing ratio (parts by weight of the resin mixture before dilution: parts by weight of the aliphatic isocyanate) is 100: 4 to 100: 10. A layered structure comprising an adhesive composition as described in any of the foregoing or subsequent patent applications. The layered structure as described in any of the foregoing or subsequent patent applications, further comprising a metal substrate. The layered structure as described in any of the foregoing or subsequent patent applications, further comprising a polyolefin substrate.